CN104718177B - Alkene is reclaimed by xylol technique - Google Patents
Alkene is reclaimed by xylol technique Download PDFInfo
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- CN104718177B CN104718177B CN201380052425.0A CN201380052425A CN104718177B CN 104718177 B CN104718177 B CN 104718177B CN 201380052425 A CN201380052425 A CN 201380052425A CN 104718177 B CN104718177 B CN 104718177B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
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- C—CHEMISTRY; METALLURGY
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- C07C7/005—Processes comprising at least two steps in series
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The method producing xylol, by (a) in the presence of alkylation catalyst, toluene and/or benzene is made to contact with methanol under conditions of effective generation alkylation effluent, this alkylation effluent comprises dimethylbenzene and byproduct mixture, and this byproduct mixture comprises water, dimethyl ether and C4Hydrocarbon；B this alkylation effluent is separated into the first fraction comprising dimethylbenzene and the second fraction comprising this byproduct mixture by ()；C () removes water to produce dry byproduct mixture from the second fraction；D the byproduct mixture of this drying of () fractional distillation is to separate the mixture into the bottom stream comprising dimethyl ether and to comprise at least some C4The tower top effluent of hydrocarbon；And (e) reclaims ethylene and propylene from this tower top effluent.
Description
Cross-Reference to Related Applications
This application claims the U.S. Patent application of the Application No. 61/711,346 submitted on October 09th, 2012 is excellent
First power and rights and interests, the disclosure of which is all incorporated herein by reference.
Technical field
The present invention relates to preparing the technique of xylol and from this technique recovery alkene with methanol alkylation benzene and/or toluene
Hydrocarbon.
Background technology
In the isomer of dimethylbenzene, xylol has extra high value, because it can be used for p-phthalic acid
Preparation, described p-phthalic acid is the intermediate in the preparation of synthetic fibers.Xylol is valuable replacement aromatic compounds
Thing, Production of Terephthalic Acid is very big for its requirement, and p-phthalic acid is the key component forming polyester fiber and resin.
Nowadays, by hydrotreated naphtha (catalytic reforming), steam cracking Petroleum or gas oil and toluene disproportionation industry system
Standby xylol.
Most of existing prepare xylene process a problem be they prepare neighbour (o)-, (m) and to (p)-
In dimethylbenzene thermodynamical equilibrium mixture, para-xylene concentration is normally only about 24wt%.Thus, separate from such mixture
Xylol usually requires that superfractionation and multistage cooling step.Above-mentioned method includes high operating cost and only has limited production
Amount.Accordingly, it has been required to provide the method that there is high selectivity for production xylol.
A kind of known method producing dimethylbenzene is included via solid acid catalyst methanol alkylation benzene and/or first
Benzene.So pass through Yashima et al. in periodical Catalysis via Cationic Exchanged Zeolite Y with methanol alkylation toluene
16th phase, the 273-280 page (1970) are open.These workers report select in 200-275 DEG C of the substantially temperature range
Property produce xylol, wherein observe the maximum yield of xylol in xylene mixture at 225 DEG C, i.e. described diformazan
About the 50% of benzene product mixtures.It is reported that, higher temperature lead to meta-xylene yield increase and to and o-Dimethylbenzene
Yield reduce.
Alternatively, ZSM-5- type zeolite, zeolite beta and silicoaluminophosphate (SAPO) catalyst have been used for this
Method.For example, United States Patent (USP) US 6,504,072 open toluene methylation process, its high selectivity prepare xylol with
And its comprise toluene and react in the presence of a catalyst with methanol, this catalyst comprises porous crystalline material, its 2,2 diformazan having
Base butane diffusion parameter is about 0.1-15sec-1120 DEG C of measurement temperature and 2,2 dimethylbutane pressure are 60 supports (8kPa).Should
Porous crystalline material is preferably medium-hole zeolite, particularly ZSM-5, its strict decatize at a temperature of at least 950 DEG C
(steaming).The oxide modifier that this porous crystalline material preferably preferably comprises phosphorus with least one is combined, to control this material
Material micro pore volume reduction amount during steaming step.
Although toluene methylation, and particularly United States Patent (USP) US6, the para-position selection of 504,072 toluene methylation process
Property, provide attractive xylol path, the method is inevitably generated substantial amounts of light (C4-) gas.These gaseous states
By-product includes alkene, particularly ethylene, propylene and butylene；Alkane, such as methane, ethane, propane and butane；And containing oxidation
Compound, such as dimethyl ether.For improving the economy of whole process, the high efficiency method reclaiming at least some these by-product is deposited
Needing so that this light gas streams is worth and can increase to higher than fuel value.The present invention relates to managing to provide said method.
According to of the present invention, it is now discovered that substantial amounts of light olefin, particularly ethylene and propylene, can be methanol/toluene
Reclaim and switch to the application in addition to being only used as fuel in alkylation process.
Content of the invention
The present invention relates to the method preparing xylol, the method comprises：A (), in the presence of alkylation catalyst, is having
Effect produce alkylation effluent under conditions of so that toluene and/or benzene is contacted with methanol, this alkylation effluent comprise dimethylbenzene with
And byproduct mixture, this byproduct mixture comprises water, dimethyl ether and C4- hydrocarbon；B this alkylation effluent is separated into by ()
The first fraction comprising dimethylbenzene and the second fraction comprising this byproduct mixture；C () removes water to produce from the second fraction
Raw dry byproduct mixture；D the byproduct mixture of this drying of () fractional distillation comprises dimethyl ether to separate the mixture into
Bottom stream and comprise at least some C4The tower top effluent of-hydrocarbon；And (e) from this tower top effluent reclaim ethylene with
And propylene.
Advantageously, it is possible to implement the method makes to flow through molecular sieve desiccant by water from described second by making the second fraction
Fraction removes, or in the embodiment replaced, is removed water from described second fraction by washing the second fraction with methanol
Go.
In preferred embodiments, the method includes making methanol to flow through molecular sieve before washing the second fraction with methanol doing
Drying prescription and the method can be implemented so that the water that dry byproduct mixture comprises is less than 100ppm weight, more preferably
20ppm weight, or less, and most preferably 1ppm weight, or less, and the dimethyl ether that this tower top effluent comprises is few
In 100ppm weight, more preferably 20ppm weight or less, and most preferably 1ppm weight or less.
In another embodiment, the byproduct mixture producing in step (a) also comprises carbon monoxide, and should
Method removes carbon monoxide from this byproduct mixture before being also included in this water removal phase (c), or in this recycling step (e)
Removed the carbon monoxide being in gas phase from this tower top effluent in the past.
In another embodiment, implement the method to make this tower top effluent is gaseous stream, and the method is also
Comprise (d) (i) to enter the tower top effluent being in gas phase of step (d) within fractional condenser and cool down this stream with from this gas
Remaining condensables are removed in phase；And (d) (ii) reclaims this gas phase, and advantageously (d) (iii) will be from step (d)
(ii) gas phase is circulated to cryogenic separation unit to go out ethylene and propylene from arbitrarily remaining tower top effluent Component seperation.In reality
Apply in scheme, ethylene and propylene can independently reclaim or reclaim together, for example, reclaimed by deep cooling, with for example further
Procedure of processing used or for sale in (for example, being polymerized).
Desirably, this cryogenic separation unit is the recovery list of refinery gas recovery unit or fluid catalytic cracking unit
Unit.
In a particularly preferred embodiment, the step (a) of the method includes providing and comprises entering of at least about 90wt% toluene
Material stream, and can implement via alkylation catalyst, this alkylation catalyst is porous crystalline material, its 2,2 dimethyl
Butane diffusion parameter is about 0.1-15sec-1, in 120 DEG C of temperature and 2,2 dimethylbutane pressure are to survey under 60 supports (8kPa)
Amount, such as medium-hole size aluminosilicate zeolites, it is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-
35, and ZSM-48, optionally it is combined with inorganic oxide matrix.
In another embodiment, it is possible to implement the method makes methanol feed the one of this toluene eject position downstream
Individual or multiple positions substep spurts into this alkylation catalyst.
Brief description
Fig. 1 is the flow process reclaiming light olefin method according to one embodiment of the application from methanol/toluene alkylation process
Figure.
Detailed Description Of The Invention
The method by preparing xylol with methanol oxidation alkylated benzenes and/or toluene for the disclosure.This alkylation
Process produces and is rich in the xylene different structure mixture of para-position, together with water and some light organic by-products, particularly dimethyl ether
And C4- alkene.This method provides the method improved, and at least separates from these light by-products and reclaims alkene for except fuel
Application in addition.
Alkylation
The alkylation adopting herein can adopt any aromatic feed comprising toluene and/or benzene, although usually
Preferably described aromatic feed contains at least 90wt%, the especially at least toluene of 99wt%.Similarly, although the charging containing methanol
Composition be not crucial, but it is generally desirable to using contain at least 90wt%, the especially at least charging of 99wt% methanol.
The catalyst adopting in alkylation is typically porous crystalline material, and in a preferred embodiment party
When being to measure at 120 DEG C of temperature and 2,2 dimethylbutane pressure of 60 supports (8kPa) in case, for 2,2 dimethylbutanes
There is about 0.1-15sec-1Diffusion parameter porous crystalline material.
As used in this article, the diffusion parameter of concrete porous crystalline material is defined as D/r2×106, wherein D is to expand
Scattered coefficient (cm2/ sec), and r is crystal radius (cm).Described diffusion parameter can be derived by absorption measurement, and premise assumes that
Plain film model describes described diffusion process.Therefore, for given adsorbent load Q, value Q/QeqWith (Dt/r2)1/2Mathematics phase
Close, wherein QeqIt is equilibrium adsorption agent load, wherein t is to reach described adsorbent load Q required time (second).Described plain film
The diagram method of model is by J.Crank in " The Mathematics of Diffusion ", Oxford University Press, Ely
House, London, be given in 1967.
Porous crystalline material is preferably the aluminosilicate zeolite of intermediate pore size.Mesopore zeolite is defined as about 5- about
Those of 7 angstroms of hole size are so that described zeolite freely sorption molecule, such as normal hexane, 3- methylpentane, benzene and to diformazan
Benzene.Another kind of Common definitions of mesopore zeolite are related to restricted index test, and it is disclosed in U.S. Patent number 4, in 016,218,
This patent is incorporated herein as reference.In this case, mesopore zeolite has the restricted index of about 1-12,
In the case of not introducing oxide modifier and any decatize with adjust catalyst diffusibility before to described boiling
Stone is individually tested.In addition to the aluminosilicate zeolite of described mesopore size, other mesopore acid metal silicate such as sial phosphoric acid
Salt (SAPO) can also be used in the inventive method.
The instantiation of suitable mesopore zeolite includes ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35
And ZSM-48, wherein ZSM-5 and ZSM-11 is particularly preferred.In one embodiment, adopt in the method for the invention
Zeolite be the ZSM-5 with least 250 silicon dioxide and alumina molar ratio, described zeolite is carried out any process with
Tested before adjusting its diffusibility.
Zeolite ZSM-5 and its routine preparation are described in U.S. Patent number 3,702,886.Zeolite ZSM-11 and its routine
Preparation is described in U.S. Patent number 3,709,979.Zeolite ZSM-12 and its routine preparation are described in U.S. Patent number 3,
In 832,449.Zeolite ZSM-23 is standby with its routine to be described in U.S. Patent number 4,076,842.Zeolite ZSM-35 and Qi Chang
Regulation is standby to be described in U.S. Patent number 4,016,245.U.S. Patent number 4,375,573 teaching ZSM-48 and its routine system
Standby.The complete disclosure of these United States Patent (USP)s is incorporated herein as reference.
Above-mentioned mesopore zeolite is preferably as relatively other xylene isomer for the inventive method,
The size and shape in their hole is more beneficial for the production of xylol.However, the conventionally form of these zeolites has exceedes this
0.1-15sec desired by inventive method-1The diffusing parameter values of scope.However, required diffusibility can pass through strict vapour
Steam zeolite with catalyst micro pore volume is carried out the controlled micro pore volume being decreased to non-steamed catalyst not less than 50%, preferably
50-90% is realizing.Inhaled by measuring the normal hexane of zeolite before and after decatize under 90 DEG C and 75 support normal hexane pressure
Attached ability is monitoring the reduction of micro pore volume.
The decatize that porous crystalline material micro pore volume required for obtaining reduces is passed through in the presence of steam at least about
950 DEG C, preferably from about 950 to about 1075 DEG C, most preferably from about 1000 to about 1050 DEG C of temperature heating material about 10 minutes to about 10
Hour, preferably 30 minutes to 5 hours carrying out.
In order to realize desired diffusibility and micro pore volume is controlled reduces it is desirable to by porous crystalline material before decatize
Material and at least one are preferably selected from the periodic table of elements (IUPAC version) ii A, IIIA, IIIB, IVA, VA, VB and Group VIA element
Oxide modifier merge.Suitably, at least one oxide modifier is selected from boron, magnesium, the oxidation of calcium, lanthanum and preferred phosphorus
Thing.In some cases, it is desirable to by porous crystalline material and more than one oxide modifier, such as phosphorus and calcium and/or magnesium
Combination merge, because it is severity so the decatize realized required for target diffusivity number may to be reduced.Present in catalyst
The total amount of oxide modifier, measures meter based on element, can be between about 0.05 and about 20wt%, such as in about 0.1 peace treaty
Weight meter between 10wt%, based on final catalyst.
In the case that modifying agent includes phosphorus, in alkylation catalyst, introduce modifying agent, by U.S. Patent number 4,
356,338,5,110,776,5,231,064 and 5, the method described in 348,643 is eligibly realized, and the entire disclosure is drawn
Enter herein as reference.Can easily realization phosphorus-containing compound process：Make porous crystalline material individually or with binding agent or
Host material combination is contacted with the solution of suitable phosphorus compound, is subsequently dried and calcines so that phosphorus is changed into its oxide form.
Contact with the phosphorus-containing compound generally temperature between about 25 DEG C and about 125 DEG C carries out about 15 minutes and about 20 hours.Connecing
In tactile mixture, the concentration of phosphorus can be between about 0.01 and about 30wt%.
Representational phosphorus-containing compound bag phosphorous oxides modifying agent being attached in catalyst of the present invention can be used for
Include by PX3、RPX2、R2PX、R3P、X3PO、(XO)3PO、(XO)3P、R3P=O, R3P=S, RPO2、RPS2、RP(O)(OX)2、RP
(S)(SX)2、R2P(O)OX、R2P(S)SX、RP(OX)2、RP(SX)2、ROP(OX)2、RSP(SX)2、(RS)2PSP(SR)2With
(RO)2POP(OR)2The derivant of the group representing, wherein R is alkyl or aryl such as phenyl, and X is hydrogen, R or halogen.These
Compound includes primary phosphine RPH2, secondary phosphine R2PH and tertiary phosphine R3P, such as butyl phosphine, phosphine oxides R3PO such as tributylphosphine oxide,
Tertiary phosphine sulfide R3PS, primary phosphonic acids RP (O) (OX)2, and secondary phosphine acid R2P (O) OX, phosphonic acids such as phenyl-phosphonic acid, corresponding sulfur derivatives are such as
RP(S)(SX)2And R2P (S) SX, the ester such as dialkyl alkylphosphonate (RO) of described phosphonic acids2P (O) H, dialkyl alkylphosphonate
(RO)2P (O) R, and dialkyl hypophosphorous acid Arrcostab (RO) P (O) R2；Phosphinous acid R2POX such as diethyl phosphinous acid, primary phosphorous
Acid esters (RO) P (OX)2, secondary phosphite ester (RO)2POX and tertiary phosphite ester (RO)3P, and their ester such as single propyl diester, dioxane
Base alkyl phosphite (RO) PR2,With alkyl dialkyl phosphite (RO)2PR.Corresponding sulfur derivatives can also be used,
Including (RS)2P(S)H、(RS)2P(S)R、(RS)P(S)R2、R2PSX、(RS)P(SX)2、(RS)2PSX、(RS)3P、(RS)PR2With
(RS)2PR.The example of phosphite ester includes NSC 6513, NSC 5284, diisopropyl phosphite, phosphorous acid butyl ester
With pyrophosphite such as pyrophosphorous acid tetra-ethyl ester.Alkyl group in the compound being previously mentioned preferably comprises 1-4 carbon atom.
Other suitable phosphorus-containing compounds include ammonium hydrogen phosphate, phosphorus Halides such as Phosphorous chloride., phosphonium bromide and iodate phosphorus, dichloro
Change alkyl phosphite, (RO) PCl2, chlorination dialkyl phosphite (RO)2PCl, dialkylphosphinochlo,idites, R2PCl, alkyl phosphono
Chlorine Arrcostab, (RO) (R) P (O) Cl, dialkyl phosphine acyl chlorides, R2P (O) Cl, and RP (O) Cl2.Applicable corresponding sulfur derivatives bag
Include (RS) PCl2、(RS)2PCl, (RS) (R) P (S) Cl and R2P(S)Cl.
Specific phosphorus-containing compound includes ammonium phosphate, ammonium dihydrogen phosphate, diammonium phosphate, diphenylphosphine chloride, phosphorous
Sour trimethyl, Phosphorous chloride., phosphoric acid, Phenylphosphine oxychlorination things, trimethyl phosphate, diphenyl phosphonic acid, diphenyl phosphonic acid, diethyl
Base thiophosphoryl chloride, acid phosphate methyl ester and other alcohol-P2O5Product.
Can be used for including the boron oxide modified dose of representative boron-containing compound being attached in catalyst of the present invention
Boric acid, methyl borate., boron oxide, sulfuration boron, boron hydride, butyl boron diformazan oxide, butyl boron dihydroxide, dimethyl boric anhydride,
Pregnancy alkylborazine, phenylboric acid, triethylborane, diborane and triphenyl borine.
Representational magnesium-containing compound includes magnesium acetate, magnesium nitrate, magnesium benzoate, propanoic acid magnesium, 2 ethyl hexanoic acid magnesium, carbonic acid
Magnesium, magnesium formate, magnesium oxalate, magnesium bromide, magnesium hydride, magnesium lactate, Magnesium dilaurate, magnesium oleate, magnesium palmitate, magnesium salicylate, Hard Fat
Sour magnesium and magnesium sulfide.
Representational calcium containing compound includes calcium acetate, calcium acetylacetonate, Calcium Carbonate, calcium chloride, calcium methoxide, aphthenic acids
Calcium, calcium nitrate, calcium phosphate, calcium stearate and calcium sulfate.
Representational include lanthanum acetate, lanthanum acetylacetone, lanthanum carbonate, lanthanum chloride, lanthanum hydroxide, nitric acid containing lanthanum compound
Lanthanum, lanthanum orthophosphate and lanthanum sulfate.
The porous crystalline material adopting in the method for the invention can be resistant to methods described employed in temperature and
The various binding agents of other conditions or host material merge.Such material include activity and inert material, such as clay,
Silicon dioxide and/or metal-oxide (as aluminium oxide).The latter can be naturally-occurring, or is in include silicon dioxide and gold
Belong to the gelatinous precipitate of hopcalite or the form of gel.The conversion using often change catalyst of the material of activity
Rate and/or selectivity, thus generally not preferred.Inert material suitably plays the effect of diluent to control turning in given method
Rate is so that product can obtain and means without employing other control reaction rates by economy and in an orderly manner.These materials
Can be incorporated in naturally occurring clay such as bentonite and Kaolin, to improve pressure under commercial operating conditions for the catalyst
Broken intensity.Described material, that is, clay, oxide etc. are as the binding agent of catalyst.Desirable to provide the crushing strength having had
Catalyst, because wish to prevent catalyst breakage from becoming powder like materials in commercial Application.These clays and/or oxide binder
Agent is typically only utilized for improving the crushing strength of catalyst.
Can with the naturally occurring clay of porous crystalline Material cladding include montmorillonite and Kaolin series those,
The Kaolin of described series inclusion change bentonite and commonly known as Dixie, McNamee, Georgia and Florida clay, or
Wherein main mineral constituent is other clays of galapectite, kaolinite, dickite, nacrite or anauxite.Such clay
Can use by the original state of original exploitation, or to use through initial calcining, acid treatment or chemical modification.
In addition to previous materials, described porous crystalline material can be combined with porous matrix material, such as silica-zirconia
Aluminum, silica-magnesia, silica-zirconium oxide, silica-thorium oxide, silica-beryllia, silicon dioxide-
Titanium dioxide and ternary composition such as silica-alumina-thoria, silica-alumina-zirconium oxide, titanium dioxide
Silicon-alumina-silica magnesium and silica-magnesiazirconia.
The relative scale of porous crystalline material and inorganic oxide matrix changes in a wide range, wherein the former content
In the range of about 1- about 90 weight % of composite, and more often, particularly when composite is by with the shape of beadlet
During formula preparation, the former content is in the range of the about 2- about 80wt% of composite.
Alkylation process can be carried out in any of reaction vessel, but usual methanol and aromatic feed with above-mentioned
Catalyst contacts, and wherein catalyst granules is disposed in one or more fluid beds.Methanol and aromatic feed each can be by
Fluidized catalyst is injected in the single stage.However, in one embodiment, methanol charging is injected in aromatic reactants
One or more positions in the position downstream of fluidized catalyst are injected into fluidized catalyst stage by stage.For example, it is possible to aromatics is entered
Material is injected into the bottom of single vertical catalyst fluidized bed, and by methanol in the centre position multiple vertically spaced apart of bed
It is injected into described bed, and product is removed from the top of bed.Alternatively, catalyst can be arranged in multiple vertical
In the catalyst bed that direction is spaced apart, aromatic feed is injected into the bottom of the first fluidized bed, and the part injection by methanol
Enter the middle part of first, and a part for methanol is injected within downstream catalyst bed or downstream catalyst bed it
Between.
The condition adopting in the alkylation stage of the inventive method is not straitly limited, but in toluene methylation
In the case of, generally include following scope：Temperature between (a) about 500 and about 700 DEG C, between e.g., from about 500 and about 600 DEG C；
Between (b) about 1 atmospheric pressure and about 1000psig (between about 100 and about 7000kPa), e.g., from about 10psig and about 200psig it
Between (between about 170 and about 1480kPa) pressure；C () at least about 0.2, the toluene molar number/methanol of e.g., from about 0.2- about 20 rubs
That number (in reactor feeds intake)；(d) for proceeding to total hydrocarbon charging of (one or more) reactor, about 0.2- is about
1000 weight (hourly) space velocity (WHSV) (" WHSV "), such as the weight (hourly) space velocity (WHSV) of about 0.5- about 500 for described aromatic reactants, and for
The weight (hourly) space velocity (WHSV) of about 0.01- about 100 for methanol reagent stage stream (stage-flows) merging, based on one or more
For total catalyst meter in reactor.
Product processes and reclaims
Product between methanol and toluene and/or benzene is alkylation effluent, and it comprises xylol and other two
Toluene isomer, vapor, unreacted toluene and/or benzene, unreacted methanol, phenol impurity, various light gaseous by-product
Such as C4- hydrocarbon, including light olefin and dimethyl ether.This alkylation effluent typically also comprises some C9+ aromatic byproducts.In addition,
If the method is carried out in the catalyst bed of fluidisation, alkylation effluent containing some entrained solid catalyst and will be urged
Agent fine powder.Therefore, leave the effluent of (final) fluidized-bed reactor, it is typically in steam phase, generally goes through integration
Cyclone separator, to remove the catalyst solid that some carry secretly and to make them return to alkylation reactor.
Alkylation effluent leaves alkylation reactor system at high temperature, typically between about 500 and about 600 DEG C,
And heat exchanger can be first passed through so that the used heat in effluent logistics can be recovered and be used for heating other technique material
Stream.It is preferable, however, that limiting any initial cooling of product stream, to keep effluent steam more than dew point, dew point is general
It is about 240 °F (116 DEG C).
After cooling down further, effluent vapor stream is fed to piece-rate system, this piece-rate system can include one
Individual or multiple fractionating columns, there unreacted methanol and aromatic compounds are recovered and are recycled to alkylation step, gently
(C4-) and weight (C9+) by-product is removed and the remainder of effluent is separated into the liquid organic phase rich in dimethylbenzene and gives up
Water stream.It is decanted off waste water from this organic product stream and typically pass through fractional crystallization or select absorption from this organic product
Xylol is reclaimed in stream.
In the method, process this light (C4-) stream is with valuable olefinic component at least reclaimed materials stream, and non-immediate
Ground conveying uses as fuel.Typically, this processes and starts including making this light stream experience drying steps to remove water, such as with dividing
Son sieves desiccant or is washed with methanol, and methanol itself is preferably with such as molecular sieve desiccant drying to remove water.It is dried
Byproduct mixture preferably comprises less than 100ppm weight water, preferably 20ppm or less weight, more preferably 1ppm or less
Weight.Optionally, before this drying steps, some of carbon monoxide formed in methylation procedure or complete can be removed
Portion.The content of water originally can suitably use Panametrics moisture analyzer, gas chromatograph, using VLE digital simulation and its
Its method known to those skilled in the art measurement.
Then, the byproduct mixture being dried is first sent to fractionating column to remove dimethyl ether from this light olefin, so that
Make alkene that reclaimer impact is minimized.Due to the shadow unfavorable to propylene in the following process of such as polyreaction etc
Ring, dimethyl ether is also harmful to the propylene product reclaiming later.This fractionating column is used for making the byproduct mixture of drying divide
Evaporate for tower top effluent, it comprises at least some C4- hydrocarbon, and almost all of dimethyl ether and C4+ hydrocarbon flows out as liquid column bottoms
Thing.For example, from the ethylene of this fractionating column and at least about 98wt% of propylene, and the about 67wt% of propane flows out in tower top
Reclaim in thing, simultaneously the C of almost 100wt% dimethyl ether and almost 100wt%4+ hydrocarbon removes in liquid bottom stream.Come
From this overhead vapours of this fractionating column, calculate by weight, it generally comprises less than about 100ppm dimethyl ether, preferably 20ppm or more
Few, more preferably calculate by weight, 1ppm or less, and some carbon monoxides, if not being previously removed, be then delivered to cold
Freeze fractional condenser, such as using the condenser of propylene freezing, and then to knockout drum, wherein vapor product phase is recovered and residual
Stay condensables to be removed and provide to this fractionating column as reflux.Ethylene refrigeration may require that condensation all is from tower top and evaporates
Divide steam, and this arranges to avoid the demand for ethylene refrigeration, thus decrease cooling cost.The number of DME in overhead vapours
Amount most preferably passes through gas chromatography analysis, the calibrated oxygenatedchemicalss with measurement such as DME etc of gas chromatogram.
Subsequently, the vapor product phase reclaiming from knockout drum is passed through cryogenic separation unit, preferably reclaims with such as refinery gas
The existing cryogenic separation unit that system or fluid catalytic cracking unit recovery system are associated, with arbitrarily residual from overhead vapours
Gas is stayed to implement separation and the recovery of ethylene and propylene.If first not removing carbon monoxide, conveying this overhead vapours phase
To before this cryogenic separation unit, remove carbon monoxide.
The dimethyl ether removing as liquid bottom stream from this fractionating column and C4+ hydrocarbon can serve as fuel or diformazan
Ether can be reclaimed with other fractionating column and be recycled to this methylation reaction device.
The carbon monoxide reclaiming from this methylation reaction effluent is also used as fuel or can be in conventional first
It is converted into methane according to following reaction in alkylation reactors:
CO+3H2→CH4+H2O
This method embodiment for processing from the light gas of toluene methylation unit is shown in Fig. 1, wherein light gas
Body (1) feeds to exsiccator (2) via optional CO recovery unit (1A).After by this exsiccator (2), this gas being dried
Mixture is delivered to fractionating column (3), and wherein this mixture is divided into overhead vapor stream (4) and liquid bottom stream (5).
Overhead vapor stream (4) is delivered to freezing fractional condenser (6), such as using the condenser of propylene freezing, and and then to knockout drum
(7), wherein vapor phase (8) is recovered and this residual condensables is removed and provides to this fractional distillation as reflux (9)
Tower.Then, vapor phase (8) via optional CO recovery unit (8A) feed to cryogenic separation unit (10) be used for reclaiming ethylene and
Propylene.
Although the present invention is disclosed by reference to specific embodiment and is illustrated, those skilled in the art
It will be understood that the present invention can provide the change not necessarily herein illustrating and change for itself, without departing from this
Bright spirit and scope.
Trade name used in this application is passed throughTMSymbol orSymbol shows, shows that its title can pass through specific business
Mark power protection, for example, they can be with various authority registered trade marks.All of patents and patent applicationss, test method are (such as
ASTM method, UL method etc.), and other the application cited literature 2, it is fully incorporated by reference, its degree makes disclosed above
The document authority quoted consistent with the present invention and above-mentioned is all allowed.When the upper limit of digital lower limit and numeral is listed in this
It is contemplated that scope is from any lower limit to any upper limit during application.
Claims (16)
1. the method producing xylol, the method comprises:
A (), in the presence of alkylation catalyst, makes toluene and/or benzene and methanol under conditions of effective generation alkylation effluent
Contact, this alkylation effluent comprises dimethylbenzene and byproduct mixture, this byproduct mixture comprise water, dimethyl ether and
C4- hydrocarbon；
B this alkylation effluent is separated into the first fraction comprising dimethylbenzene and comprise this byproduct mixture second by ()
Fraction；
(c) by make the second fraction flow through molecular sieve desiccant or by wash the second fraction with the methanol of unitary part and from
Second fraction removes water to produce the byproduct mixture comprising the drying less than 100ppm water；
D the byproduct mixture of this drying of () fractional distillation is to separate the mixture into the bottom stream comprising dimethyl ether and bag
Containing at least some C4The tower top effluent of-hydrocarbon；And
E () reclaims ethylene and propylene from this tower top effluent.
2. the method for claim 1, is also included in and makes methanol flow through molecular sieve desiccant before washing the second fraction with methanol.
3. the method for claim 1 wherein that this tower top effluent comprises the dimethyl ether less than 100ppm weight.
4. the method for claim 1 wherein that the byproduct mixture producing in (a) also comprises carbon monoxide.
5. the method for claim 4, removes carbon monoxide from this byproduct mixture before being also included in water removal phase (c).
6. the method for claim 4, removes carbon monoxide from this tower top effluent before being also included in recycling step (e).
7. the method for claim 1 wherein that this tower top effluent is vapor phase stream.
8. the method for claim 1, also comprises
D the tower top effluent being in vapor phase of () (i) step (d) enters within fractional condenser and cools down this stream with from this gas
Remaining condensables are removed in phase；And
D () (ii) reclaims this gas phase.
9. the method for claim 8, also comprises
D () (iii) vapor phase from step (d) (ii) is passed through to cryogenic separation unit with from arbitrarily remaining tower top effluent
Isolate ethylene and propylene in component, and optionally further include step (d) (iv) by ethylene and propylene cryogenic separation.
10. the method for claim 9, wherein this cryogenic separation unit are refinery gas recovery system or fluid catalytic cracking list
First recovery system or one of ethylene plant's recovery system or Pyrolytic cracking furnace system or its combination in any.
The method of 11. claim 9, also comprises to remove carbon monoxide from this vapor phase.
The method of 12. claim 10, also comprises to remove carbon monoxide from this vapor phase.
13. the method for claim 1 wherein to provide toluene with the feed steam comprising at least 90 weight % toluene.
14. the method for claim 1 wherein that this alkylation catalyst is when in 120 DEG C of temperature and 2,2 dimethyl of 8kPa
Under butane pressure, during measurement, the diffusion parameter for 2,2 dimethylbutanes is 0.1-15sec-1Porous crystalline material.
The method of 15. claim 14, wherein this alkylation catalyst are medium-hole size aluminosilicate zeolites, and it is selected from
ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48, are optionally combined with inorganic oxide matrix.
16. the method for claim 1 wherein that methanol is fed spray by the one or more positions substep in toluene eject position downstream
Inject this alkylation catalyst.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261711346P | 2012-10-09 | 2012-10-09 | |
| US61/711,346 | 2012-10-09 | ||
| PCT/US2013/061345 WO2014058609A1 (en) | 2012-10-09 | 2013-09-24 | Recovery of olefins from para-xylene process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104718177A CN104718177A (en) | 2015-06-17 |
| CN104718177B true CN104718177B (en) | 2017-03-08 |
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| CN201380052425.0A Active CN104718177B (en) | 2012-10-09 | 2013-09-24 | Alkene is reclaimed by xylol technique |
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| Country | Link |
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| US (1) | US20140100402A1 (en) |
| CN (1) | CN104718177B (en) |
| WO (1) | WO2014058609A1 (en) |
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| CN104334515A (en) | 2012-04-19 | 2015-02-04 | 沙特***石油公司 | Combined heavy reformate dealkylation-transalkylation process for maximizing xylenes production |
| SG11201610150PA (en) * | 2014-06-04 | 2017-01-27 | Dalian Chemical Physics Inst | Method for preparing p-xylene and co-producing propylene with high selectivity |
| JP6389284B2 (en) | 2014-06-30 | 2018-09-12 | エクソンモービル・ケミカル・パテンツ・インク | Method for producing para-xylene |
| US9469579B2 (en) | 2014-06-30 | 2016-10-18 | Exxonmobil Chemical Patents Inc. | Process for the production of xylenes |
| US20160060187A1 (en) * | 2014-08-26 | 2016-03-03 | Exxonmobil Chemical Patents Inc. | Treatment of Off-Gas in the Production of Para-Xylene by the Methylation of Toluene and/or Benzene |
| CN108473883A (en) | 2015-12-30 | 2018-08-31 | 环球油品公司 | Alkene is improved using aliphatic compounds cracking reactor and BTX is produced |
| CN106039762B (en) * | 2016-07-06 | 2018-08-31 | 山西潞安煤基合成油有限公司 | A kind of method and device for improving low-temp methanol and washing prewashing methanol extraction effect |
| WO2018057125A2 (en) | 2016-09-22 | 2018-03-29 | Exxonmobil Chemical Patents Inc. | Use of light gas by-products in the production of paraxylene by the methylation of toluene and/or benzene |
| US20180179455A1 (en) * | 2016-12-27 | 2018-06-28 | Uop Llc | Olefin and btx production using aliphatic cracking and dealkylation reactor |
| CN106669818B (en) * | 2016-12-27 | 2019-08-30 | 西安元创化工科技股份有限公司 | It is a kind of to be alkylated preparation to the preparation method and applications of methyl-ethyl benzene catalyst |
| US10173950B2 (en) | 2017-01-04 | 2019-01-08 | Saudi Arabian Oil Company | Integrated process for the production of benzene and xylenes from heavy aromatics |
| US10035742B1 (en) | 2017-05-26 | 2018-07-31 | Saudi Arabian Oil Company | Process for maximizing xylenes production from heavy aromatics for use therein |
| US10252958B2 (en) | 2017-05-26 | 2019-04-09 | Saudi Arabian Oil Company | Process for xylene production with energy optimization |
| US10464868B2 (en) | 2017-05-26 | 2019-11-05 | Saudi Arabian Oil Company | Process for maximizing production of xylenes from heavy reformate without purge |
| WO2019112769A1 (en) | 2017-12-05 | 2019-06-13 | Exxonmobil Chemical Patents Inc. | Xylene production processes and systems |
| US10696609B2 (en) | 2018-10-15 | 2020-06-30 | Saudi Arabian Oil Company | Integrated process for maximizing production of para-xylene from full reformate |
| US10894755B2 (en) | 2018-10-15 | 2021-01-19 | Saudi Arabian Oil Company | Integrated process for optimum production of para-xylene |
| US10501389B1 (en) | 2018-10-25 | 2019-12-10 | Saudi Arabian Oil Company | Process and system for the production of para-xylene and benzene from streams rich in C6 to C12+ aromatics |
| US11691933B2 (en) * | 2019-03-28 | 2023-07-04 | Exxonmobil Chemical Patents Inc. | Processes and systems for converting benzene and/or toluene via methylation |
| US11827579B2 (en) * | 2019-03-28 | 2023-11-28 | ExxonMobil Technology and Engineering Company | Processes for converting benzene and/or toluene via methylation |
| US11643375B2 (en) * | 2019-03-28 | 2023-05-09 | Exxonmobil Chemical Patents Inc. | Processes for converting benzene and/or toluene via methylation |
| CN114166696B (en) * | 2020-09-11 | 2023-08-18 | 中国科学院大连化学物理研究所 | Molecular sieve catalyst diffusion property evaluation method |
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| WO2014058609A1 (en) | 2014-04-17 |
| US20140100402A1 (en) | 2014-04-10 |
| CN104718177A (en) | 2015-06-17 |
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